CN1047043A - 丁二烯二聚反应用催化剂的制备方法 - Google Patents

丁二烯二聚反应用催化剂的制备方法 Download PDF

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CN1047043A
CN1047043A CN90102600A CN90102600A CN1047043A CN 1047043 A CN1047043 A CN 1047043A CN 90102600 A CN90102600 A CN 90102600A CN 90102600 A CN90102600 A CN 90102600A CN 1047043 A CN1047043 A CN 1047043A
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杜安·E·希顿
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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Abstract

适合于将二烯(如丁二烯)二聚成4-乙烯基环己烯的催化剂是在一种存在一种易氧化金属(例如锡)的有机溶剂中使(1)氯化铁和亚硝酸钠或(2)亚硝酰基氯化铁与(3)一氧化碳反应制备的。所述催化剂溶液在使用前应进行过滤以除掉颗粒物质。用两种方法中的任一种所生成的催化剂都含有最低量的还原剂和副产物,然而采用氯化铁和亚硝酸钠的反应是优选的。该催化剂在没有丁二烯单体存在下可以单独贮存，同时可保持稳定性和活性。

Description

人们知道，配合物-亚硝酰基羰基铁[Fe（NO）2（CO）2]可使丁二烯二聚合成乙烯基环己烯（VCH）。据信，该催化活性是由于Fe（NO）2片段所致。已知的制备这种配合物的方法要求在电解池中以及丁二烯存在的情况下使[Fe（NO）2Cl]2还原，或使一氧化氮（NO）在铁和FeCl3的混合物上反应。据信，亚硝酰基铁催化剂可就地生成并使用，达到二聚的目的。美国专利4，238，301中可查到这些方法。另一篇美国专利4，234，454披露了在使各种共轭二烯二聚的体系中，通过使锰、锌或锡一起与铁、钴或镍的亚硝酰基卤化物化合生成相应的亚硝酰基金属来制备各种亚硝酰基金属催化剂溶液的方法。较早的美国专利3，510，533披露了共轭二烯类与正烯丙基二亚硝酰基铁配合物的二聚反应及其制备方法。包括μ，μ′-二卤四亚硝酰基二铁还原反应在内的几种方法也已提供。
本技术领域已知的亚硝酰基金属化合物的还原方法有许多缺点。这些缺点是：（1）亚硝酰基金属化合物的还原反应要求在有丁二烯存在的情况下进行，（2）许多还原剂本身将使丁二烯聚合，（3）还原剂会带来污染以及（4）催化剂溶液不能贮存，也不能保持其活性。
本发明方法的二聚产物本身可用，或作为其它产物的中间体。例如，4-VCH可以（1）氯化成杀虫剂，（2）氧化成苯甲酸，（3）酸式催化剂存在的情况下与硫化氢反应成含硫树脂，以及（4）在紫外光下与硫化氢反应成β-巯基乙基环己烷。
适于二烯烃聚合成二聚物（例如丁二烯聚合成4-VCH）的催化剂，可在一种有机溶剂中和一氧化碳存在的情况下，通过用一种易氧化金属（例如锡）使亚硝酰基氯化铁还原而制成。据信，该催化剂是亚硝酰基羰基铁。这种催化剂的性能与其它亚硝酰基铁催化剂系一样好。类似的钴和镍化合物将生成类似的催化剂，但其活性不如铁化合物好。
另一种，也是一种优选的方法是在一种易氧化金属存在的情况下，使FeCl2和NaNO2与一氧化碳在一种溶剂中反应来制备催化剂。该催化剂的还原剂和副产物含量最低。这样生成的催化剂可在没有丁二烯单体存在的情况下单独贮存，同时保持其稳定性和活性。
通常，本发明的催化剂适合于将共轭二烯烃类二聚成为环状产物。虽然以丁二烯作为制备4-VCH的例子，但其它的共轭二烯类也同样可被环化。因此，异丙烯和其它共轭二烯属烃也可被二聚成环状化合物。
虽然氯化亚铁是形成本发明的催化剂用的配合物的优选化合物，但其它化合物也可用来制备这类催化剂。这样，例如[Fe（NO）2Cl]2和FeCl3都可用于制备该催化剂。类似的钴和镍化合物也可用于制备类似的催化剂，但这类催化剂的活性不如铁催化剂高。
例如，除锡之外的其它可用的还原剂还包括锌、锰和镁，或可在还原反应中使用一种电解池。
例如，可使用的有机溶剂包括醚类，象二乙醚类和二丁醚类，四氢呋喃（THF），二甘醇甲醚，乙二醇甲醚;有机酯类，象碳酸亚丙酯，碳酸亚乙酯和乙酸乙酯;以及腈类，象乙腈和苄腈。
该反应所采用的压力以足以将一氧化碳保持在有机溶剂中为度，例如1～1，000磅/英寸（表压6，900kPa）。
可使用的温度在室温至250℃范围内，最好为25～100℃。
反应时间随所投物料量、压力和温度而变化。通常，时间在1～48小时范围是可操作的，但时间不超过24小时一般足以完成该反应。
丁二烯的二聚条件对于本技术领域是人所共知的，而且使用本发明的催化剂是可操作的。温度范围为20°～175℃;压力范围为大气压～1，000磅/英寸（表压6，900kPa）;反应在10分钟～24小时范围内进行。
如下实施例为该催化剂制备和使用的典型实例：
实施例1
催化剂制备
将15.00克5%的[Fe（NO）Cl]的四氢呋喃（THF）溶液和1.12克锡粉加入一个20毫升高压釜中。然后用CO气吹洗该反应器（除去空气），搅拌物料的同时加压至75磅/英寸（表压518kPa）。该反应器温度维持在大约25℃，同时搅拌约5小时，之后，将反应器卸压，并过滤溶液以除去不溶物，例如锡或锡化合物。
实施例A（对照）
重复实施例1的方法，不同之处在于用氮气代替CO气，所有其它参数均相同。
实施例B（对照）
将10.12克5%的[Fe（NO）2Cl]2的THF溶液，45.95克THF和1.28克正锌烷＊加入300毫升的高压釜中。本试验中不加锡粉。然后用CO气吹洗该反应器并升至50磅/英寸（表压345kPa），加热至70℃，搅拌的同时使反应大约5.5小时。然后将该反应器卸压。
＊正辛烷用作气相层析的分析标准。
实施例2
在实施例1的反应器中，将1.03克锡粉加入10.0克5%的[Fe（NO）2Cl]2的二甘醇二甲醚溶液中。然后用CO气吹洗反应器，搅拌物料的同时升压至90磅/英寸（表压620kPa）。温度保持在25℃，同时连续搅拌48小时，之后，将反应器卸压并过滤溶液。
实施例3
在实施例1和2所使用的相同反应器中加入0.36克FeCl2，0.19克NaNO2，0.38克锡粉及18.75克作为溶剂的二甘醇二甲醚。然后用CO气吹洗反应器，并用CO气升至75磅/英寸（表压518kPa），同时搅拌物料。温度保持在120℃，同时连续搅拌20小时，之后，使该反应器卸压并过滤溶液。
实施例4
在另一试验中，采用碳酸亚丙酯作溶剂，使用与实施例1和2相同的反应器。反应剂的用量如下：0.37克FeCl2，0.2克NaNO2。1.19克锡粉以及作为溶剂的1.8克碳酸亚丙酯。操作方法与实施例3相同，压力为90磅/英寸（表压620kPa），温度为120℃，反应时间14小时。
下列实施例说明催化剂的用途。
实施例5
二聚反应
将实施例1中所制备的催化剂溶液放入一300毫升的高压釜中，在其中加入180克丁二烯，用氮气将该反应器加压至300磅/英寸（2070kPa）。连续搅拌该反应器，使反应持续一段时间以足以完成丁二烯的转化，时间的长短由反应进行期间的间隔采样来决定。该实施例的反应时间大约14小时。
实施例6，7和8
按照实施例5的方法，分别使用实施例2、3和4中所制备的催化剂进行二聚反应。
使用上述催化剂制备方法所获得的结果示于下表：
催化剂    条件/结果
（实施例编号）    催化剂1    时间    转化率    选择性
（克）    （小时）    （%）    （%）
1    10.0    15    64    100
A    10.0    15    19    100
B    2    14    2    -
2    10.0    14    66    100
3    8.0    14    51    100
4    10.0    14    91    100
1.所用重量为催化剂溶液之重量。
2.实施例B所制备的催化剂的总量全部用于该二聚反应。
3.二甘醇二甲醚（34.15克）作为稀释剂加入该催化剂。

Claims (10)

1、一种制备适用于共轭二烯属烃二聚的催化剂的方法，所述方法包括使(a)铁、钴或镍的氧化物和碱金属亚硝酸盐或(b)铁、钴或镍的亚硝酰基氯化物与(c)一氧化碳在它们的溶剂中以及在易氧化金属存在的情况下反应。
2、权利要求1中所述的方法，其中所述可氧化金属从锡、锌、锰和镁中选取。
3、权利要求2中所述的方法，其中所述用于反应的溶剂为一种有机溶剂，而共轭二烯属为丁二烯。
4、权利要求3中所述的方法，其中所述有机溶剂为一种有机醚、酯或腈。
5、权利要求4中所述的方法，其中所述有机醚为环醚或乙二醇醚;所述有机酯为碳酸亚烃酯，而所述有机腈为乙腈。
6、权利要求5中所述的方法，其中所述乙二醇醚为乙烯或二甘醇的烷基醚，而环醚为四氢呋喃。
7、上述权利要求中任一项所述的方法，其中所述反应是在大气压（100kPa）～1，000磅/英寸（表压6，900kPa）的压力下和室温～175℃的温度范围中进行的。
8、权利要求1中所述的方法包括在一种溶剂中和有金属锡存在的情况下使氯化铁和亚硝酸钠与一氧化碳反应。
9、按照上述权利要求中的任一项的方法制备催化剂组合物。
10、一种丁二烯二聚的方法采用了权利要求9的催化剂组合物。
CN90102600A 1989-05-08 1990-05-07 丁二烯二聚反应用催化剂的制备方法 Expired - Fee Related CN1023977C (zh)

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JPH02303540A (ja) 1990-12-17
KR900017658A (ko) 1990-12-19
CN1023977C (zh) 1994-03-16
AU5477890A (en) 1990-11-08
AU621221B2 (en) 1992-03-05
US4973568A (en) 1990-11-27
EP0397266A2 (en) 1990-11-14
DE69001319T2 (de) 1993-07-22
ATE88109T1 (de) 1993-04-15
EP0397266A3 (en) 1990-12-27
BR9002126A (pt) 1991-08-13
EP0397266B1 (en) 1993-04-14
CA2016187A1 (en) 1990-11-08
ES2040033T3 (es) 1993-10-01
DE69001319D1 (de) 1993-05-19
AR244576A1 (es) 1993-11-30
DK0397266T3 (da) 1993-05-24

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